TW201630050A - Integration of laser processing with deposition of electrochemical device layers - Google Patents

Abstract

A method of fabricating an electrochemical device in an apparatus may comprise: providing an electrochemical device substrate; depositing a device layer over the substrate; applying electromagnetic radiation to the device layer in situ to effect one or more of surface restructuring, recrystallization and densification of the device layer; repeating the depositing and the applying until a desired device layer thickness is achieved. Furthermore, the applying may be during the depositing. A thin film battery may comprise: a substrate; a current collector on the substrate; a cathode layer on the current collector; an electrolyte layer on the cathode layer; and a lithium anode layer on the electrolyte layer; wherein the LLZO electrolyte layer has a crystalline phase, no shorts due to cracks in the LLZO electrolyte layer, and no highly resistive interlayer at the interface between the electrolyte layer and the cathode layer.

Description

Integration of laser processing and deposition of electrochemical element layers [Reciprocal Reference of Related Applications]

The application claims the benefit of U.S. Provisional Application Serial No. 62/073,818, filed on Jan. 31, 2014, the entire disclosure of which is hereby incorporated by reference.

Embodiments of the present disclosure are generally directed to tools and methods for fabricating electrochemical components, and more particularly, but not exclusively, integration of laser processing and electrochemical element layer deposition.

An electrochemical element such as a thin film battery (TFB) comprises a stack of layers including a collector layer, a cathode (positive electrode) layer, a solid electrolyte layer, and an anode (negative electrode) layer. The challenge in fabricating such components is to create the crystallinity, crystals required to achieve satisfactory performance of the completed component, when considering the type of material used in such components, ceramics, dielectrics, metal oxides, phosphorus oxynitride, and the like. Material layer of phase, surface morphology, material density and pinhole density. These materials have low surface mobility and high activation energy for forming materials having the desired characteristics. Component performance, throughput, manufacturability, and cost will depend on the suitability of layers that produce satisfactory crystallinity, phase, and density. And the degree of convenience. There is a clear need for tools and methods for fabricating component layers having the desired material properties.

The present disclosure describes deposition and processing tools and methods for improving the characteristics of electrochemical element layers, including such energy storage elements as thin film batteries (TFBs), electrochromic elements, and the like. Layer properties considered include crystallinity, surface morphology, material density, and pinhole density. The hardware and method include integrating the laser processing of the component layer with the layer deposition, wherein the treatment is in situ, and for the material type and deposition method (physical vapor deposition (PVD), chemical vapor deposition (chemical vapor deposition) Vapor deposition; CVD), atomic layer deposition (ALD), etc. are both unknown.

According to some embodiments, a method of fabricating an electrochemical component in an apparatus can include: providing an electrochemical component substrate; depositing a component layer over the substrate; applying electromagnetic radiation to the component layer in situ to achieve surface reconstruction of the component layer, One or more of recrystallization and densification; this deposition is repeated and applied until the desired component layer thickness is achieved.

According to some embodiments, an apparatus for fabricating an electrochemical component can include: a first system for depositing a layer of components over a substrate; and a second system for applying electromagnetic radiation to the layer of components to achieve a surface weight of the component layer One or more of structure, recrystallization, and densification; a third system for repeating the deposition and a fourth system for repeating the application.

According to some embodiments, a thin film battery may include: a substrate; a current collector on the substrate; a cathode layer on the current collector; an electrolyte layer on the cathode layer; and a lithium anode layer on the electrolyte layer; The LLZO electrolyte layer has a crystalline phase, which is not short-circuited due to cracks in the LLZO electrolyte layer, and has no high-resistance interlayer at the interface between the electrolyte layer and the cathode layer.

100‧‧‧First TFB component structure

101‧‧‧Substrate

102‧‧‧Cathode Collector

103‧‧‧Anode collector

104‧‧‧ cathode

105‧‧‧ Electrolytes

106‧‧‧Anode

107‧‧‧Encapsulation layer

200‧‧‧Second exemplary TFB component structure

201‧‧‧Substrate

202‧‧‧ Collector layer

203‧‧‧Anode collector layer

204‧‧‧ cathode layer

205‧‧‧ electrolyte layer

206‧‧‧ anode layer

207‧‧‧ blanket encapsulation layer

208‧‧‧Adhesive pad

209‧‧‧Adhesive pad

300‧‧‧Vertical deposition system along the line

301‧‧‧Modularization chamber

302‧‧‧Vacuum pump

303‧‧‧Loading brake

310‧‧‧Substrate

321‧‧‧Sedimentary source

322‧‧‧Sedimentary source

323‧‧‧Sedimentary source

324‧‧‧Sedimentary source

331‧‧ ‧ laser processing tools

332‧‧‧Laser processing tools

333‧‧ ‧ laser processing tools

334‧‧ ‧ laser processing tools

401‧‧‧ steps

402‧‧‧Steps

403‧‧‧Steps

404‧‧‧Steps

501‧‧‧Steps

502‧‧‧Steps

503‧‧‧Steps

600‧‧‧Deposition tools

601‧‧‧vacuum chamber

602‧‧‧ Sputtering target

603‧‧‧Substrate carrier

604‧‧‧Substrate

605‧‧‧vacuum pump system

606‧‧‧Cell and process gas delivery systems

607‧‧‧Additional power supply

608‧‧‧electrode

700‧‧‧ Equipment

702‧‧‧Substrate carrier

704‧‧‧Electromagnetic energy

706‧‧‧Optical components

708‧‧‧ movable mirror

710‧‧‧ Locator

712‧‧‧Optical column

714‧‧‧Rectifier

716‧‧‧ Optical unit

718‧‧‧Electromagnetic energy

720‧‧‧ energy column

722‧‧‧Processing area

724‧‧‧ emitter

726‧‧‧ Controller

800‧‧‧Substrate

801‧‧‧ top surface

802‧‧‧ bottom surface

803‧‧‧Substrate carrier

820‧‧‧ Cover

825‧‧‧Fiber optic cable

826‧‧‧Fiber laser assembly

835‧‧‧Transparent optical aperture

900‧‧‧heat treatment equipment

902‧‧‧Work surface

904‧‧‧Laser

906‧‧‧Exposed areas

908‧‧‧Directed energy flow

910‧‧‧ energy distributor

912‧‧‧Rotate

914‧‧‧Support

916‧‧‧reflection flow

918‧‧‧ Collector

920‧‧‧Communication

922‧‧‧Roller

924‧‧‧ center line

926‧‧‧ Controller

These and other aspects and features of the present disclosure will become apparent to those of ordinary skill in the <RTIgt; A cross-sectional view of an example; a second cross-sectional view of a second example of a TFB component in accordance with some embodiments; and a third top-down view of an in-line processing system in accordance with some embodiments 4 is a first process flow for laser assisted deposition of electrochemical element layers in accordance with some embodiments; and FIG. 5 is a second process for laser assisted deposition of electrochemical device layers in accordance with some embodiments 6 is a schematic illustration of an example of a sputter deposition tool that may be used in the line processing system of FIG. 3 in accordance with some embodiments; and FIG. 7 is a line processing system that may be used in FIG. 3 in accordance with some embodiments. Schematic diagram of an example of a first laser processing tool; 8 is a schematic illustration of an example of a second laser processing tool that may be used in the line processing system of FIG. 3 in accordance with some embodiments; and FIG. 9 is a line processing system that may be used in FIG. 3, in accordance with some embodiments. A schematic diagram of an example of a third laser processing tool.

Embodiments of the present disclosure will now be described in detail with reference to the accompanying drawings, which are provided as an illustrative example of the present disclosure. The drawings provided herein include illustrations of components and components that are not drawn to scale. The following drawings and examples are not intended to limit the scope of the disclosure to a single embodiment, but other embodiments are possible by the interchange of some or all of the elements. In addition, some of the elements of the present disclosure, which may be implemented in part or in full, using known elements, will only describe those parts of such known elements that are necessary for the understanding of the present disclosure, and such The detailed description of other parts of the components is known to avoid obscuring the present disclosure. In the present disclosure, an embodiment showing a single element is not to be considered as limiting; rather, the present disclosure is intended to cover other embodiments including a plurality of the same elements, and vice versa, unless explicitly stated otherwise herein. In addition, any terminology in the present disclosure is not intended to be in a Further, the present disclosure encompasses known equivalents of known elements that are referred to herein by way of example.

The present disclosure describes deposition and processing tools and methods for improving the characteristics of electrochemical element layers, including such energy storage elements as thin film batteries (TFBs), electrochromic elements, and the like. Layer properties considered include crystallinity, surface morphology, material density, and pinhole density. The hardware and methods are agnostic to both material type and deposition method (physical vapor deposition, chemical vapor deposition, atomic layer deposition, etc.). Methods for improving the material properties of component layers include imparting energy to the deposition system to overcome the energetics associated with surface mobility and crystallization - it is proposed herein to integrate laser processing into processing hardware and fabrication methods. In addition, it is also possible to limit the heat to the desired layer during deposition and thereby limit the wide spread of heat - also by minimizing the challenges of integrating laser processing into processing hardware and manufacturing methods. The thermal budget for the overall component. A schematic representation of a linear deposition system in which laser processing is integrated is illustrated in Figure 3, and a process flow is shown in Figures 4 through 5, which are described in more detail below.

In-situ modification of the crystallinity and phase of the cathode material can result in simplified process integration and improved component performance, for example, lower thermal budget during post-deposition annealing, resulting in lower stack stress and thus better yield and longer term Component durability. The better surface morphology (of the cathode) and the zero pinhole density (of the electrolyte) can result in better component yield and cause a reduction in manufacturing cost per unit. If electrolyte deposition can achieve zero pinhole density at lower layer thicknesses, this can result in significant manufacturing cost reduction due to lower requirements for the thickness of the deposited film for a given throughput. In addition, This reduction in electrolyte thickness can also result in improved component performance via the lower internal impedance of the component. The improvement in the material density of the cathode layer (this density is equal to the energy content of the component) can result in a higher energy content for a given layer thickness. This improvement in mass density and energy density can be used to produce components having high volume and weight energy densities.

1 shows an illustration of a first TFB element structure 100 having a cathode current collector 102 and an anode current collector 103 formed on a substrate 101, followed by a cathode 104, an electrolyte 105, and an anode 106. One or more of the component layers are formed using integrated laser processing and deposition in accordance with embodiments of the present disclosure; although the components can be fabricated using cathodes, electrolytes, and anodes in reverse order. Note that a layer is shown on top of the substrate 101, which is an optional insulating layer for electrically isolating the anode current collector from the cathode current collector when a conductive substrate such as a metal is used. Further, a cathode current collector (CCC) and an anode current collector (ACC) may be separately deposited. For example, a cathode current collector can be deposited before the cathode and an anode current collector can be deposited after the electrolyte. The component may be covered by an encapsulation layer 107 to protect the environmentally sensitive layer from oxidants. It should be noted that in the TFB elements shown in FIG. 1, the element layers are not necessarily drawn to scale. The structure of Figure 1 is representative of the components formed using the mask.

2 shows a representation of a second exemplary TFB element structure 200 comprising a substrate 201 (eg, glass), a current collector layer 202 (eg, Ti/Au), a cathode layer 204 (eg, LiCoO ₂ ), electrolyte layer 205 (eg, LiPON), anode layer 206 (eg, Li, Si), anode current collector layer 203 (eg, Ti/Au), bonding pads for anode current collectors and cathode current collectors, respectively (eg , aluminum) 208 and 209, and blanket encapsulation layer 207 (eg, polymer, tantalum nitride), wherein one or more of the component layers are integrated laser processing and deposition using embodiments in accordance with the present disclosure form. It should be noted that in the TFB elements shown in FIG. 2, the element layers are not necessarily drawn to scale. The structure of Figure 2 is representative of the use of direct patterning of layers - such as those formed using laser ablation.

The specific TFB component structures provided above with reference to Figures 1 and 2 are merely examples, and it is contemplated that embodiments of the present disclosure are applicable to a variety of different TFB structures.

In addition, a variety of different materials can be used for different TFB component layers. For example, the substrate may be a glass substrate, and the cathode layer may be a LiCoO ₂ layer (a layer deposited by, for example, radio frequency (RF) sputtering, direct current (DC) sputtering, etc.), and the anode layer may be Li The metal layer (layer deposited by, for example, evaporation, sputtering, etc.), and the electrolyte layer may be a LiPON layer (layer deposited by, for example, radio frequency sputtering or the like). However, it is contemplated that the present disclosure is applicable to a wider range of TFBs containing different materials. Furthermore, the deposition techniques for laser processing according to embodiments for such layers may include various deposition techniques such as physical vapor deposition, plasma enhanced chemical vapor deposition (PECVD), Reactive sputtering, non-reactive sputtering, RF sputtering, multi-frequency sputtering, electron and ion beam evaporation, thermal evaporation, chemical vapor deposition, atomic layer deposition, etc.; this deposition method can also be based on non-vacuum Deposition methods such as plasma spraying, spray pyrolysis, slit coating, screen printing, and the like. For a physical vapor deposition sputter deposition process, the process can be an alternating current (AC), direct current, pulsed direct current, radio frequency, high frequency (HF) (eg, microwave) process, or a combination of the above processes. .

Examples of the material of the different element layers of the TFB may include one or more of the following materials. The substrate may be tantalum, tantalum nitride on Si, glass, polyethylene terephthalate (PET), mica, metal foil such as copper, and the like. The anode current collector and the cathode current collector may be one or more of Ag, Al, Au, Ca, Cu, Co, Sn, Pd, Zn, and Pt, and the metals may be alloyed and/or present in different materials. An adhesive layer of one or more of a plurality of layers and/or including Ti, Ni, Co, refractory metal, and superalloy. The cathode may be LiCoO ₂ , V ₂ O ₅ , LiMnO ₂ , Li ₅ FeO ₄ , NMC (NiMnCo oxide), NCA (NiCoAl oxide), LMO (LixMnO ₂ ), LFP (LixFePO ₄ ), LiMn spinel, and many more. The solid electrolyte may be a lithium conductive electrolyte material including materials such as LiPON, LiI/Al ₂ O ₃ mixture, LLZO (LiLaZr oxide), LiSiCON, Ta ₂ O ₅ and the like. The anode can be Li, Si, lithium lanthanum alloy, lithium lanthanum hydride, Al, Sn, C, etc. and other low potential Li salts such as Li ₄ Ti ₅ O ₁₂ .

The anode/negative electrode layer may be a pure lithium metal or may be a Li alloy in which Li is alloyed with, for example, a metal such as tin or a semiconductor such as germanium. The Li layer can be about 3 [mu]m thick (depending on the cathode and capacitance balance) and the encapsulation layer can be 3 [mu]m or thicker. The encapsulating layer can be a polymer/polyparaphenyl group and a multilayer of metal and/or dielectric. It should be noted that between the formation of the Li layer and the encapsulation layer, this portion should be maintained in an inert or very low humidity environment such as argon or in a drying chamber; however, after deposition of the blanket encapsulation layer, it will be relaxed Requirements for inert environments. The anode current collector can be used to protect the Li layer that allows laser ablation outside of the vacuum, and can relax the requirements for an inert environment.

In addition, metal current collectors on both the cathode and anode sides may need to act as a protective barrier against shuttle lithium ions. In addition, the anode current collector may need to act as a barrier layer to the oxidant from the environment (eg, H ₂ O, O ₂ , N _{2 ,} etc.). Therefore, the collector metal can be selected to have minimal reactivity and miscibility with lithium contact in "two directions", that is, "two directions" - that is, Li moves into the metal current collector to form a solid solution and vice versa. Also. In addition, metal current collectors can be selected for their low reactivity and diffusivity to oxidants from the environment. Some potential candidates suitable for the first requirement may be Cu, Ag, Al, Au, Ca, Co, Sn, Pd, Zn, and Pt. For some materials, it may be necessary to manage the thermal budget to ensure no reaction/diffusion between the metal layers. Alloys can be considered if a single metal element does not meet two requirements. In addition, if the single layer does not meet the two requirements, a double (or multiple) layer can be used. In addition, the adhesive layer may additionally be used in combination with a layer of one of the above refractory or non-oxidized layers - for example, a Ti adhesion layer bonded to Au. The current collector can be deposited by (pulsed) direct current sputtering of a metal target to form a layer (for example, a metal such as Cu, Ag, Pd, Pt, and Au, a metal alloy, a metalloid or carbon black). In addition, there are other options for forming a protective barrier layer for shuttle lithium ions, such as a dielectric layer, and the like.

For example, Figure 3 shows a top down plan view of the vertical deposition system 300 along the line. The system can include a plurality of modular chambers 301 having components for vacuum deposition of various layers - a vacuum pump 302 , a load gate 303 , through which the substrate 310 is transferred to a plurality of deposition sources 321 - 324 The front chamber/catheter and the laser processing tools 331 to 334 (for example, a sputter deposition source). The deposition source can be used for different component layers or, if desired, the deposition source can be used for multiple depositions of the same material to accumulate the thickness of a particular component layer. Although the deposition system is shown as having a vertical substrate orientation, an in-line deposition system having a horizontally oriented substrate can also be used in the embodiments. Moreover, in some embodiments, non-vacuum deposition and laser processing can be used; in some embodiments, a mixture of vacuum and non-vacuum modules can be present within the system.

The strategic location of the laser processing tool relative to the deposition source is shown in Figure 3, which is used to provide energy to the deposited layer to improve the quality of the deposited material. There are a variety of configurations for laser processing integration. The number and location of the laser processing tools may depend, in several factors, on the layer thickness (deposition rate from the source), the desired energy level of the induced effect, and the carrier speed. There are two different modes for integrating the laser processing tool with the component layer deposition source. The first mode is real mine A shot assist mode in which the laser beam is directed to a sputter/deposition area on the substrate/component stack surface (source 3/laser 3 in Figure 3). The second mode is the in-situ but post-deposition heat treatment (surface reconstruction/recrystallization/densification) of the deposited layer (Source 1, Source 2, and Source 4/Laser 1, Laser 2, and Laser 4 in Figure 3). ). In the second case, the laser processing tool can be positioned between the two deposition sources such that the laser beam extends beyond the sputter/deposition plasma region.

In addition, by virtue of the gate valve/restricted aperture between the modules with independent vacuum pumps, the gas environment-pressure and composition can be independently controlled within different processing modules along the line system. For example, maintaining a higher oxygen partial pressure within the laser processing module during annealing of the LiCoO ₂ (LCO) device layer can provide improved material properties from -15% to 100% of the O ₂ chamber environment. Enhance the formation of the high temperature phase of LCO - the desired degree of crystallinity. If this method is used to deposit a LiCoO ₂ cathode - a relatively thick component layer of approximately 30 microns to 50 microns - multiple continuous depositions and laser annealing may be required, and the partial pressure of oxygen in the laser annealing module will remain Higher than the partial pressure of oxygen in the deposition module. In the deposition of LLZO electrolytes - component layers up to approximately 3 microns thick - may require multiple successive depositions and laser annealing, and the oxygen partial pressure in the laser annealing module will remain at the oxygen level in the deposition module The level of high pressure.

The laser can be selected as follows. First, the wavelength is selected based on the optical properties of the deposited layer (light absorption based on its n value and k value versus frequency) and, if selectivity is required, the wavelength is far from the maximum value of the k value of the surrounding material. Second, based on the required "depth and duration" of the thermal load (to a higher pulse frequency to maximize localization) and the desired dissipation/propagation selection pulse frequency Rate and exposure time (or rasterization speed). CW lasers can also be considered. Third, the power is chosen to achieve the desired effect, such as surface reconstitution/crystalline phase/crystallinity/densification of the layer. While this specification can focus on such battery materials, the methods described herein are equally applicable to other material types, deposition methods, and applications.

An example of a laser selection for processing a LiCoO ₂ material layer is a solid-state Nd:YAG frequency-doubled 532 nm laser, and another example is a fiber laser frequency doubling to about 0.5 micron.

4 and 5 provide an example of a process flow for depositing electrochemical element layers in accordance with an embodiment. As shown in FIG. 4, the process for fabricating an electrochemical component can include: providing an electrochemical component substrate/element stack (401); depositing a component layer (402) over the substrate/component stack; after deposition, The processing element layer is shot to effect surface reconstruction/recrystallization/densification of the element layer (403); this deposition and laser processing is repeated until the desired component layer thickness is achieved (404). The electrochemical element can be a TFB, an electrochromic element, or other element. The component layer can be a layer of LiCoO ₂ material, LLZO material, or other electrochemical component material. If this method is used to deposit a LiCoO ₂ cathode - a relatively thick element layer of approximately 30 microns to 50 microns - multiple sequential depositions and laser annealing may be required.

As shown in FIG. 5, the process for fabricating an electrochemical component can include: providing an electrochemical component substrate/component stack (501); depositing a component layer over the substrate/component stack and during deposition, the laser processing component The layer promotes surface reconstitution/crystallization/densification of the component layer (502); this deposition and laser processing is repeated until the desired component layer thickness is achieved (503). The electrochemical element can be a TFB, an electrochromic element, or other element. The component layer can be a layer of LiCoO ₂ material, LLZO material, or other electrochemical component material.

In an embodiment, the element layer can be exposed to pulses of electromagnetic radiation as described below. A plurality of processing regions are typically defined on the substrate and the plurality of processing regions are sequentially exposed to pulses. In one embodiment, the pulses may be pulses of laser light, each pulse having a wavelength between about 200 nm and about 1200 nm, such as about 532 nm, as delivered by a frequency doubled Nd:YAG laser. In an embodiment, a CO ₂ laser can be used to transfer energy. Other wavelengths such as infrared, ultraviolet, and other visible wavelengths can also be used. The pulses may be delivered by one or more sources of electromagnetic radiation, and the pulses may be delivered via optical or electromagnetic components to shape or otherwise modify the selected characteristics of the pulses.

The component layer can be gradually heated to a temperature that allows surface reconstitution/recrystallization/densification by treatment with laser light pulses. Each pulse of the laser light may have sufficient energy to heat a portion of the stack of elements, each pulse of the laser light impinging on a portion of the stack of elements to activate surface reconstruction/recrystallization/densification of the element layer. For example, for a 30 ns laser pulse, each pulse can deliver between about 0.1 J/cm ² and about 1.0 J/cm ² ; and, more importantly, depending on the pulse duration, the fluence needs to be Adjustments are made in the range between several mJ/cm ² to several J/cm ² . A single pulse strikes the surface of the substrate and transfers most of this pulse energy as heat to the substrate material. The first pulse of the impact surface impinges on the solid material and heats the material to the activation temperature. Depending on the energy delivered by the first pulse, the surface region can be heated to a depth of between about 6 nm and about 60 nm. Upon reaching the surface, a pulse impacts the activating material, delivering thermal energy propagating through the activating material into the surrounding material, activating more of the component layers. In this manner, successive pulses of electromagnetic radiation can be formed in front of the active material through each element of the continuous pulse. The activated portion of the element layer undergoes surface reconstruction/recrystallization/densification to form an element layer having improved material properties.

Moreover, in an embodiment, the spacing between pulses can be long enough to allow the energy imparted by each pulse to be completely dissipated. Therefore, each pulse completes the microannealing cycle. This pulse can be delivered to the entire substrate at one time or to several portions of the substrate each time.

Moreover, in an embodiment, the thermal budget for annealing of the component layers can be managed to reduce thermal stresses between adjacent component layers in the component layers or in the component stack. For example, a first laser pulse to a particular region of the wafer can preheat the wafer to a temperature between the ambient temperature and the annealing temperature that forms the preheating region, and then the second laser pulse can increase a portion of the preheating region The temperature is to the annealing temperature, wherein the annealed portion is surrounded by the preheating material to reduce thermal stress. Using this method, the annealed front can span the element layer, typically having a preheating zone prior to annealing the front to reduce thermal stress in the element layer being annealed, and typically has a portion under the portion that is annealed A preheating zone that reduces thermal stress between adjacent layers in the component stack. In addition, when annealing the top layer of the stack, thermal budget management can be used to minimize the amount of heat deposited into the stack of component layers, thereby reducing the temperature experienced by the underlying layers in the stack. The latter is important, for example, to achieve annealing of the crystalline anode layer over the LiPON electrolyte without altering the amorphous state of the LiPON electrolyte - an example of such a crystalline anode material is a Li salt material such as Li ₄ Ti ₅ O ₁₂ , The material has a lower chemical potential versus Li than the cathode material.

The laser-assisted deposition proposed herein can enable deposition of a LLZO electrolyte layer by creating a desired crystalline phase without or minimizing the deleterious effects of deposition annealing after formation of the electrolyte material. First, the LLZO of the crystalline phase (different from the microcrystalline or amorphous phase) has the highest ionic conductivity of one cubic LLZO with an ionic conductivity of about 10E-4 S/cm. If it is high temperature, post-deposition annealing is necessary to achieve this crystalline phase, and it is expected that this layer will react with the cathode at the electrolyte/cathode interface to form a Li ion intercalation reaction (at the anode) that will negatively affect the operation of the cell. - an interlayer of the electrochemical reaction between Li ions and electrons at the electrolyte interface). Depending on the sintering temperature and the particular cathode material, etc., the by-product of the reaction between the LLZO and the cathode material will be electrochemically inert (blocking) or in some embodiments, the reaction by-product has an ionic conductivity less than that of the LLZO electrolyte layer. Several times (or more times) the ionic conductivity; and in embodiments, the reaction by-product has an ionic conductivity that is one order of magnitude (or more orders of magnitude) lower than the ionic conductivity of the LLZO electrolyte layer. (The reaction interlayer between the cathode and LLZO will have an ionic conductivity in the embodiment that is less than the amorphous phase of LiPON or LLZO - typically less than or equal to 10E-7 S/cm.) Furthermore, post-deposition annealing can be expected Will generate thermal stress (heating and cooling of the annealing process) The cycle creates stress induced cracks in the layer and thus provides a short circuit path when depositing a subsequent Li anode. Thus, if the LLZO layer can be formed with the desired degree of crystallinity during deposition without or with very little heat treatment, such detrimental conditions can be avoided. It is contemplated that a laser heating process using a laser of the appropriate wavelength and pulse duration selection as described herein can limit heating to the necessary layer (LLZO) to achieve the desired crystallization and phase formation reactions without affecting Interfaces and/or substrates that minimize interface reaction and stress formation. At the same time, this method provides a simple and improved densification pathway with a thinner growth layer and avoids the need to anneal the entire stack thickness. Thus, in situ laser assisted deposition can overcome the limitations of conventional layer fabrication and formation methods.

For example, according to an embodiment, a thin film battery may include: a substrate; a current collector on the substrate; a cathode layer on the current collector; an electrolyte layer on the cathode layer; and a lithium anode layer on the electrolyte layer; Wherein the LLZO electrolyte layer has a crystalline phase, no short circuit due to cracks in the LLZO electrolyte layer, and no high resistance interlayer at the interface between the electrolyte layer and the cathode layer.

The logic of LCO layer formation is similar to the logic of LLZO layer formation. It is expected that in-situ densification and phase formation of LCO with minimal internal stress and surface/block rupture will result in improved component performance and throughput. It is expected that a dense LCO film with minimal stress will result in a better theoretical number of capacity usage versus the theoretical limit of LCO. Lower stress and better surface morphology when the battery undergoes volume expansion and cyclic contraction Better component performance and stability will result during subsequent electrodeposition and during battery operation.

Returning to Figure 3, an example of a deposition tool that can be used in a deposition system along the line is a plasma-assisted sputter deposition system such as that shown in Figure 6. FIG. 6 shows a schematic illustration of an example of a deposition tool 600 that is provided for a deposition method in accordance with an embodiment of the present disclosure. The deposition tool 600 includes a vacuum chamber 601, a sputtering target 602, and a substrate carrier 603 for holding and moving the substrate 604 through the sputter deposition tool 600 during sputter deposition. The chamber 601 has a vacuum pump system 605 for controlling the pressure in the chamber and process gas delivery system 606. In addition, FIG. 6 shows an additional power source 607 that can be coupled to either the substrate or the target, or to the target and the substrate, or directly coupled to the chamber using the electrode 608. Pulp. An example of the latter is a power source 607, which is a microwave power source that is directly coupled to the plasma using an antenna (electrode 608); however, the microwave energy can be provided to the plasma in many other ways, such as at a remote plasma source. The microwave source for direct coupling to the plasma can include an electron cyclotron resonance (ECR) source.

A plurality of power sources can be connected to the sputtering target in FIG. Each target power supply has a matching network for processing radio frequency (RF) power supplies. The filter is operative to enable operation at different frequencies using two power supplies connected to the same target/substrate, wherein the filter acts to protect the target/substrate power supply operating at lower frequencies from being attributed to higher Damage caused by frequency power. Similarly, A plurality of power sources can be connected to the substrate. Each power source connected to the substrate has a matching network for processing radio frequency (RF) power supplies. In addition, a blocking capacitor can be coupled to the substrate carrier 603 to induce different carrier/chamber impedances to modulate the self-bias of the surface within the processing chamber, including the target and substrate, and thereby induce different variations in growth kinetics. (1) sputtering rate on the target and (2) kinetic energy of the adsorbed atom. The capacitance of the blocking capacitor can be adjusted to vary the self-bias at different surfaces within the process chamber, importantly the self-bias of the substrate surface and the target surface.

Although Figure 6 shows a chamber configuration with a horizontal planar target and substrate, the target and substrate can be held in a vertical plane for integration into a vertical line system such as that shown in Figure 3. The target 602 can be a rotating or oscillating cylindrical target as shown, a double rotating cylindrical target can also be used, or the target can have some other non-planar or planar configuration. Here, the term "oscillation" is used to mean a limited rotational motion in either direction such that the solid state electrical connection to the target suitable for transmitting radio frequency power can be adjusted. In addition, the matching box and filter can be combined into a single unit for each power source. One or more of these variations may be used in a deposition tool in accordance with some embodiments.

According to some embodiments, different combinations of power sources in the deposition system of Figure 6 can be used by coupling a suitable power source to a substrate, target, and/or plasma. Depending on the type of plasma deposition technique used, the substrate and target power supply can be any combination of direct current, pulsed direct current (pDC) power, and AC power (having lower than RF, typically less than 1) The frequency of MHz), the RF power supply, etc. are selected. Additional power supplies can be selected from pDC, AC, RF, microwave, remote plasma sources, and more. RF power can be supplied in continuous wave (CW) or burst mode. Additionally, the target can be configured as a high-power pulsed magnetron (HPPM). For example, the combination can include dual RF power at the target, pulsed DC and RF at the target, and the like. (The dual RF at the target is best suited for insulating the dielectric target material, while the pulsed DC and RF or DC and RF at the target can be used for conductive target materials. In addition, it can be based on the substrate base. The substrate bias power type is selected to what extent and the desired effect.)

As discussed above, it is contemplated that deposition and laser processing hardware and processing methods are not known for the method of material deposition. Thus, the deposition hardware and method described with reference to Figure 6 is only one of many deposition options.

Returning to Figure 3, an example of a laser processing tool in an in-line deposition system that can be used for in situ heat treatment of electrochemical element layers is shown in Figures 7-9. Typically, the laser processing tool may have one or more of the following features: one or more lasers, such as Nd: YAG, CO ₂ laser and an optical fiber; a laser spot size and shape change; for example, a rotating polygon, Laser beam movement on the surface of the electrochemical element such as an galvanometer scanner; pulse train capability; and thermal budget management capabilities.

FIG. 7 is a schematic cross-sectional view of device 700 in accordance with some embodiments. The device typically includes a chamber 701 that has a movable chamber The substrate carrier 702 is passed therethrough. The source of electromagnetic energy 704 can be disposed in the chamber, or in another embodiment, the source of electromagnetic energy 704 can be disposed outside of the chamber and electromagnetic energy can be delivered to the chamber via a window in the chamber wall . The source of electromagnetic energy 704 delivers one or more beams of electromagnetic energy 718, such as a laser beam, from one or more emitters 724 toward optical assembly 706. One or more beams of electromagnetic energy may be formed into an electromagnetic energy train 720 for the optical assembly 706 of the electromagnetic assembly, directing the energy train 720 toward the rectifier 714. Rectifier 714 directs energy column 720 toward processing region 722 of substrate support 702 or toward a processing region of the substrate disposed on the substrate support.

The optical assembly 706 can include a movable mirror 708, which can be a mirror, and an optical string 712 aligned with the mirror 708. Mirror 708 is mounted to positioner 710 which, in the embodiment of Fig. 7, rotates to direct the reflected beam toward the selected position. In other embodiments, the mirror can be translated rather than rotated, or the mirror can be translated or rotated simultaneously. The optical column 712 forms and shapes the energy pulses reflected by the mirror 708 from the energy source 704 into a desired energy train 720 for processing the substrate on the substrate carrier 702.

Rectifier 714 can include a plurality of optical units 716 to direct energy column 720 toward processing region 722. The energy train 720 is incident on a portion of the optical unit 716 that changes the direction of propagation of the energy train 720 to a direction generally perpendicular to the substrate support 702 and the processing region 722. As long as the substrate disposed on the substrate carrier 702 is flat The energy train 720 exits the rectifier 714, which also travels generally perpendicular to the substrate.

Optical unit 716 can be a lens, a cymbal, a mirror, or other means for changing the direction of propagating radiation. The continuous processing region 722 is processed by moving the optical component 706 such that the mirror 708 directs the energy column 720 toward the continuous optical unit 716 and is pulsed by electromagnetic energy from the energy source 704.

In one embodiment, the rectifier 714 can be a two-dimensional array of optical units 716 that extend over the substrate carrier 702. In this embodiment, optical component 706 can be actuated to direct energy column 720 to any processing region 722 of substrate carrier 702 by reflecting energy column 720 toward optical unit 716 above the desired location. In another embodiment, the rectifier 714 can be a row of optical units 716 having a length greater than or equal to the size of the substrate carrier. A row of optical units 716 can be located over a portion of the substrate, and an energy column 720 sweeps through the optical unit 716 to process (if desired) portions of the substrate below the rectifier 714; and then the row of optical units 716 can be moved to cover Adjacent columns of the processing area, the entire substrate is processed progressively in columns.

The energy source 704 of Figure 7 shows four separate beam generators, as in some embodiments, individual pulses in the pulse train may overlap. Multiple beams or pulse generators can be used to generate overlapping pulses. In some embodiments, pulses from a single pulse generator can also become overlapping by using appropriate optics. The use of one or more pulse generators will depend on the precise characteristics of the energy columns required for a given embodiment.

The interdependence of energy source 704, optical component 706, and rectifier 714 can be controlled by controller 726. The controller may be coupled to energy source 704 entirely or to each energy generator of energy source 704; and the controller may control power delivery to the energy source, or energy output from the energy generator, or control this Both. Controller 726 may also be coupled to an actuator (not shown) for moving optical assembly 706 and an actuator (not shown) for moving rectifier 714, if desired. Additionally, substrate carrier 702 can be moved into and out of the plane of the drawing along the process line during laser heat treatment; moreover, in some embodiments, there is no rectifier in the laser processing tool.

A second example of a laser processing tool in an in-line deposition system that can be used for in situ heat treatment of electrochemical element layers is shown in FIG. Figure 8 is a schematic cross-sectional view of a laser processing tool in accordance with some embodiments. 8 shows the relative movement between the output of the fiber-free laser beam assembly 826 and the substrate 800, through which the light is passed through the fiber optic cable 825 into the chamber and across the substrate 800 on the substrate carrier 803 to process the substrate. The laser processing tool, although it is possible to use the substrate carrier to move along the process line during the laser processing to move the substrate carrier into and out of the plane of the drawing. Additionally, if desired, the motion of the substrate carrier relative to the fiber optic cable can be provided by a combination of motion of the substrate and motion of the output of the fiber laser assembly.

For pulses less than about 20 milliseconds in duration, the substrate may not have the same temperature at the top surface 801 and the bottom surface 802 until after the pulse is terminated. Therefore, it is better to directly The illuminated and heated top surface 801 performs an optical measurement of the thermal response to the illumination. Top surface 801 can be monitored via transparent optical apertures 835 that align with the surface of substrate 800 (via apertures in substrate carrier 803) rather than via transparent optical apertures 835 that align with bottom surface 802. The processing system is configured with a transparent optical aperture 835 that is part of a cover 820 that also supports the fiber optic cable 825. The thermal response of the top surface 801 of the substrate 800 can be monitored by high temperature measurements at a wavelength to increase the accuracy of the temperature measurement, which is different from the wavelength of light emitted from the fiber laser. Detecting different wavelengths reduces the likelihood that illumination from reflection or scattering from the fiber laser will be misinterpreted as heat generated from the top surface of the substrate 800.

Since the pulse from the fiber laser may be as short as 2 nanoseconds, the light detected by the pyrometer may not indicate the equilibrium temperature of the surface. Further processing may be required to determine the actual temperature of the surface during or after exposure to the laser. Alternatively, the original optical signal can be used and this raw optical signal is related to the resulting film, the optimum properties of the dopant, or other surface characteristics. In Fig. 8, fiber lasers assembly 826 outputs light inside the processing chamber. In an alternate embodiment, the fiber laser output 826 can be located outside of the processing chamber and light is transferred into the chamber via the transparent window. In another alternative embodiment, the fiber laser output 826 can occupy a separate portion of the chamber where the output is still protected from process conditions. Separating the output of the fiber laser 826 from the processing region has the added advantage of preventing deposition, etching, or other reactions, such deposition, Etching or other reactions will adversely affect the transmission efficiency of the optical radiation up to the surface of the substrate 800.

Fiber lasers can produce short wavelength light (<0.75 μm or <0.5 μm in the embodiment) while at longer wavelengths (between about 0.5 μm and 1.2 μm or between 0.75 μm and 1.2 μm) A pyrometry measurement is performed to separate the heating wavelength from the monitored wavelength. The fiber optic cable 825 shown in Figure 8 may or may not be part of the doped laser cavity, but may be an undoped fiber used to transfer light from the laser cavity into the chamber.

A third example of a laser processing tool in an in-line deposition system that can be used for in situ heat treatment of electrochemical element layers is shown in FIG. Figure 9 is a perspective view of a thermal processing apparatus 900 in accordance with another embodiment. Work surface 902 provides a workspace for positioning a substrate that can be moved as shown schematically by roller 922. The laser 904 produces an directional energy stream 908 of radiant energy along a path generally parallel to the plane defined by the working surface 902 and toward the energy distributor 910. The energy distributor 910 can be a reflector or a refractor and, as indicated by arrow 912, deflects the directed energy stream 908 toward the current collector 918, which is an optical element, or a collection of such optical elements, this collection The pieces collect the energy of the directed energy stream 908 and direct the collected energy toward the substrate. The energy distributor 910 typically has a motor that rotates the energy distributor at a desired rate. The energy distributor 910 is supported by the support member 914 at a desired location above the work surface 902.

The energy distributor 910 sends a directed energy reflective stream 916 toward the current collector 918 that transmits a reflected stream 916 toward the working surface 902 with a positive alternating current 920 that is an directional energy flow perpendicular to the working surface 902. Current collector 918 has a reflective surface that faces working surface 902. The reflective mask has a shape that reflects the directional energy such that the distance "x" from the exposed region 906 of the working surface 902 of the centerline 924 of the working surface 902 is substantially greater than the reflection above the plane defined by the working surface 902. The angular extent of the energy flow 916 is proportional to 6. Current collector 918 can have a plurality of mirrors, a continuous segmented mirror surface, or a continuous curved mirror.

The substrate can be continuously translated through device 900 under current collector 918, while pulses of energy are directed to the substrate via rotational energy distributor 910. The substrate can also be translated step by step through the device. Optical devices may also be included, if desired, to limit divergent light as the divergent light approaches the energy distributor; and if desired, the energy distributor may have focusing optics such as curved reflective or refractive surfaces to compensate for the different path lengths Differential divergence or coherent loss. Controller 926 controls the rotation of energy splitter 910, the pulse rate of laser 904, and the translation of the substrate to achieve the desired processing. The rotation of the energy splitter 910, the pulse rate of the energy source 904, and the translation of the substrate can be synchronized by the controller 926 to match the edge of one of the processing regions 906 of the substrate to the edge of the adjacent processing region by The processing regions are joined together to achieve uniform processing of the substrate, particularly when the rectangular energy field applied to each processing region is uniform.

In an alternate embodiment, a high repetition rate radiation source can be coupled to the two movable mirrors to position a radiation field for processing different target regions of the substrate. When the radiation source pulse is modulated, the movable mirror can sweep through a pattern such that the target area can be processed according to any desired pattern, wherein the rate of movement of the mirror is related to the repetition rate of the radiation source.

The method according to the embodiment can be used in the heat treatment of the electrochemical element layer using a tool as shown in Fig. 9. First, a treatment zone is defined on the layer of electrochemical elements to be treated. The processing region is typically defined in accordance with the size and shape of the energy field to be applied to each processing region. The location of each processing region is likewise defined as needed to provide a processing region boundary, an overlap of portions of the processing region, or a substantially precise alignment of the spacing between processing regions. As described above in connection with Fig. 9, the rectangular processing region can be aligned by the sync pulse rate, the rotation rate of the polygon mirror, and the translation rate of the substrate.

Second, the substrate having the electrochemical element layer is positioned on the work surface such that a subset of the processing regions are exposed to the energy device. The energy device delivers energy via an energy dispenser to a working surface on which the substrate is placed. Positioning the substrate can be accomplished by moving the work platform on which the substrate is placed or by directly operating the substrate using a carrier or a rolling tray.

Third, a plurality of energy pulses are delivered to the energy distributor near the substrate. The energy pulse is a laser pulse. For example, a laser pulse of 20 ns to 50 ns in duration may be delivered with an average cross-sectional energy density of about 0.5 J/cm ² with a standard deviation of about 3% or less. The energy pulses can be delivered at a constant interval between pulses or at longer intervals defining a burst of pulses with shorter intervals.

Fourth, the energy distributor receiving the plurality of energy pulses rotates at a constant rate to deliver energy pulses to each of the processing regions of the subset. As the energy splitter rotates, the energy splitter changes the direction of energy pulse propagation, receives energy pulses along a constant optical path, and redirects these energy pulses to an optical path that changes with the rotation of the energy splitter. The energy distributor can be reflective or refracting, such as mirrors, cymbals, lenses, and the like. The energy distributor can include optical elements that, if a flat substrate is used, compensate for the non-linearity when projecting the rotational pattern of the energy distributor onto a flat surface of the substrate.

The laser processing tools and methods described above with reference to Figures 7 through 9 are only three examples of many laser processing tools and methods that can be used in the systems and processes of the present disclosure. method.

Although embodiments of the present disclosure have been specifically described with reference to an in-line system for fabricating electrochemical components with deposition and integrated laser processing and process methods along the line system, further embodiments include deposition with associated cluster tools and A clustering tool that integrates laser processing and process methods.

Although the embodiments of the present disclosure have been described with reference to processes and tools including laser processing for fabricating TFBs, it is contemplated that the teachings and principles of the present disclosure are also applicable to the processing of other electrochemical components such as electrochromic elements.

Although the embodiments of the present disclosure have been specifically described with reference to certain embodiments of the present disclosure, it is obvious to those skilled in the art that the form and details can be carried out without departing from the spirit and scope of the present invention. Changes and modifications.

300‧‧‧Vertical deposition system along the line

301‧‧‧Modularization chamber

302‧‧‧Vacuum pump

303‧‧‧Loading brake

310‧‧‧Substrate

321‧‧‧Sedimentary source

322‧‧‧Sedimentary source

323‧‧‧Sedimentary source

324‧‧‧Sedimentary source

331‧‧ ‧ laser processing tools

332‧‧‧Laser processing tools

333‧‧ ‧ laser processing tools

334‧‧ ‧ laser processing tools

Claims (15)

A method of fabricating an electrochemical component in an apparatus, comprising the steps of: providing an electrochemical device substrate; depositing a component layer over the substrate; applying electromagnetic radiation in situ to the component layer to achieve a surface of the component layer One or more of reconstitution, recrystallization, and densification; repeating the step of depositing and the step of applying until a desired component layer thickness is achieved. The method of claim 1, wherein the applying step is after the step of depositing. The method of claim 1 wherein the step of applying is during the step of depositing. The method of claim 1, wherein the electrochemical element substrate comprises a component layer stack on the surface of the electrochemical element substrate. The method of claim 1, wherein the electrochemical component is a thin film battery. The method of claim 1, wherein the step of applying electromagnetic radiation is laser processing. The method of claim 1, wherein the element layer is a layer of LiCoO ₂ material. The method of claim 1, wherein the component layer is a layer of LLZO material. The method of claim 1, wherein the step of applying comprises laser pulse train annealing. The method of claim 1, wherein the step of applying comprises thermal budget management. An apparatus for fabricating an electrochemical component, comprising: a first system for depositing a component layer over the substrate; and a second system for applying electromagnetic radiation to the component layer to achieve a surface of the component layer One or more of reconstitution, recrystallization, and densification; a third system for repeating the deposition step, and a fourth system for repeating the step of applying. The device of claim 11, wherein the device is an along-line device. The device of claim 11, wherein the second system comprises a laser and the fourth system comprises a laser. The apparatus of claim 11 wherein the step of applying is during the step of depositing. A thin film battery comprising: a substrate; a current collector on the substrate; a cathode layer above the current collector; an electrolyte layer on the cathode layer; and a lithium anode layer on the electrolyte layer; wherein the LLZO electrolyte layer has a crystalline phase due to the LLZO electrolyte The crack in the layer is free of short circuits and there is no high resistance interlayer at the interface between the electrolyte layer and the cathode layer.